Method of using dithiazine to inhibit corrosion

ABSTRACT

Corrosion of metallic tubulars in an oil, gas or geothermal well may be inhibited by introducing into the well a dithiazine of the formula: 
                         
wherein R is selected from the group consisting of a C 1  to C 10  saturated or unsaturated hydrocarbyl group or a C 1  to C 10  ω-hydroxy saturated or unsaturated hydrocarbyl group. The dithiazine may be isolated from a whole spent fluid formed by reaction of hydrogen sulfide and a triazine. Alternately, the whole spent fluid containing the dithiazine may be introduced into the well. In addition, the dithiazine or whole spent fluid may be formulated with at least one component selected from alkyl, alkylaryl or arylamine quaternary salts; mono or polycyclic aromatic amine salts; imidazoline derivative or a quaternary salt thereof; a mono-, di- or trialkyl or alkylaryl phosphate ester; or a monomeric or oligomeric fatty acid.

FIELD OF THE INVENTION

The invention relates to methods of inhibiting corrosion in metallic surfaces during treatment of an oil or gas well by introducing into the oil or gas well a dithiazine.

BACKGROUND OF THE INVENTION

During the production life of an oil or gas well, the production zone within the well is typically subjected to numerous treatments. Corrosion of metallic surfaces, such as downhole tubulars, during such treatments is not uncommon and is evidenced by surface pitting, localized corrosion and loss of metal. Metallic surfaces subject to such corrosion are carbon steels, ferritic alloy steels, and high alloy steels including chrome steels, duplex steels, stainless steels, martensitic alloy steels, austenitic stainless steels, precipitation-hardened stainless steels and high nickel content steels.

Further, aqueous fluids, such as those used in drilling and completion, have a high salt content which causes corrosion. Gases, such as carbon dioxide and hydrogen sulfide, also generate highly acidic environments to which metallic surfaces become exposed. For instance, corrosion effects from brine and hydrogen sulfide are seen in flow lines during the processing of gas streams. The presence of methanol, often added to such streams to prevent the formation of undesirable hydrates, further often increases the corrosion tendencies of metallic surfaces.

Further, naturally occurring and synthetic gases are often conditioned by treatment with absorbing acidic gases, carbon dioxide, hydrogen sulfide and hydrogen cyanide. Degradation of the absorbent and acidic components as well as the generation of by-products (from reaction of the acidic components with the absorbent) results in corrosion of metallic surfaces.

The use of corrosion inhibitors during well treatments to inhibit the rate of corrosion on metal components and to protect wellbore tubular goods is well known. Commercial corrosion inhibitors are usually reaction mixtures or blends that contain at least one component selected from nitrogenous compounds, such as amines, acetylenic alcohols, mutual solvents and/or alcohols, surfactants, heavy oil derivatives and inorganic and/or organic metal salts.

Many conventional corrosion inhibitors used to reduce the rate of acid attack on metallic surfaces and to protect the tubular goods of the wellbore are becoming unacceptable in oilfield treatment processes. For instance, many conventional corrosion inhibitors have become unacceptable due to environmental protections measures that have been undertaken. In some instances, such as in stimulation processes requiring strong acids, high temperatures, long duration jobs and/or special alloys, the cost of corrosion inhibitors may be so high that it becomes a significant portion of total costs.

Efforts have been undertaken to find alternative corrosion inhibitors which are cost effective and which are capable of controlling, reducing or inhibiting corrosion.

SUMMARY OF THE INVENTION

Corrosion of metallic tubulars in an oil, gas or geothermal well may be inhibited from forming by introducing into the well a dithiazine of the formula:

wherein R is selected from the group consisting of a C₁ to C₁₀ saturated or unsaturated hydrocarbyl group or a C₁ to C₁₀ ω-hydroxy saturated or unsaturated hydrocarbyl group.

The dithiazine may be isolated from a whole spent fluid formed by reaction of hydrogen sulfide and a triazine, such as 1,3,5-tris(hydroxyethyl)-hexahydro-s-triazine, in a hydrogen sulfide scavenger gas scrubbing operation.

Alternately, the whole spent fluid containing the dithiazine may be introduced into the well without isolation of the dithiazine.

Synergistic effects on inhibition of corrosion have further been noted when the isolated dithiazine or whole spent fluid is formulated with at least one component selected from alkyl, alkylaryl or arylamine quaternary salts; mono or polycyclic aromatic amine salts; imidazoline derivatives; a mono-, di- or trialkyl or alkylaryl phosphate ester; or a monomeric or oligomeric fatty acid.

BRIEF DESCRIPTION OF THE DRAWINGS

In order to more fully understand the drawings referred to in the detailed description of the present invention, a brief description of the drawings is presented, in which:

FIGS. 1-7 demonstrate the effectiveness as whole spent fluids (WSF), formulated with additives defined herein.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

Corrosion is inhibited during the treatment of a subterranean formation which is penetrated by an oil, gas or geothermal well by introducing into the well a dithiazine of the formula:

wherein R is selected from the group consisting of a C₁ to C₁₀ saturated or unsaturated hydrocarbyl group or a C₁ to C₁₀ ω-hydroxy saturated or unsaturated hydrocarbyl group.

In a preferred embodiment, wherein R is —R¹—OH, wherein R¹ is an alkylene group, preferably a C₁-C₆—OH group, most preferably —CH₂CH₂—OH.

The amount of dithiazine introduced into the well is an amount sufficient to inhibit corrosion of the base materials, especially iron, of tubulars in the well.

The dithiazine is preferably that obtained from the homogeneous fluid which is produced during a hydrogen sulfide scavenger gas scrubbing operation. In such scrubbing operations, a scavenger is introduced to a stream of liquid hydrocarbons or natural gas (sour gas) which contains hydrogen sulfide. In addition, such gas scrubbing operations remove hydrogen sulfide from oil production streams as well as petroleum contained in storage tanks, vessels, pipelines, etc. The scavenger is most commonly a water soluble triazine known in the art. The production of dithiazines during a scrubbing operation using a triazine as scavenger is reported in U.S. Pat. No. 6,582,624. The method disclosed in this patent is reported to dithiazine solid deposits, especially at high operating temperatures, typically greater than 300° C. Typically, dithiazines remain part of the whole spent fluid resulting from the scrubbing operation. Whole spent fluid is typically discarded.

In the method described herein, the dithiazine resulting from the scrubbing operation may be introduced into a gas, oil or geothermal well where it functions as a corrosion inhibitor. The whole spent fluid may be introduced to the well or the dithiazine.

Alternatively, the dithiazine may be isolated from the whole spent fluid by processes known in the art. The dithiazine may then be introduced as a component of an aqueous treatment fluid into the well. The fluid may be water such as fresh water, brackish water, brine as well as salt-containing water solutions such as sodium chloride, potassium chloride and ammonium chloride solutions.

In a preferred embodiment, dithiazine (either isolated dithiazine or whole spent fluid) may be formulated with at least one other component selected from the groups:

-   -   (a) an alkyl, hydroxyalkyl, alkylaryl or arylamine quaternary         salt;     -   (b) a mono or polycyclic aromatic amine salt;     -   (c) an imidazoline derivative;     -   (d) a mono-, di- or trialkyl or alkylaryl phosphate ester; a         phosphate ester of hydroxylamines; and phosphate esters of         polyols; or     -   (e) a monomeric or oligomeric fatty acid.

When formulated, the volume ratio of dithiazine to the additive component is typically between from about 1:0.5 to about 1:2.0, more typically between from about 1:0.8 to about 1:1. The dithiazine is formulated with the additive by adding the additive to the whole spent fluid or by adding the additive to an alcoholic (for example methanol) solution containing the dithiazine.

Exemplary of the alkyl, hydroxyalkyl, alkylaryl or arylamine quaternary salts are those alkylaryl and arylamine quaternary salts of the formula [N⁺R¹R²R³R⁴][X⁻] wherein R¹, R², R³ and R⁴ contain one to 18 carbon atoms, X is Cl, Br or I. In a preferred embodiment, any or all of the R¹, R², R³ and R⁴ are a C₁-C₆ alkyl group or a hydroxyalkyl group wherein the alkyl group is preferably a C₁-C₆ alkyl or an alkyl aryl such as benzyl. The mono or polycyclic aromatic amine salt with an alkyl or alkylaryl halide include salts of the formula [N⁺R¹R²R³R⁴][X⁻] wherein R¹, R², R³ and R⁴ contain one to 18 carbon atoms, X is Cl, Br or I.

Typical quaternary ammonium salts are tetramethyl ammonium chloride, tetraethyl ammonium chloride, tetrapropyl ammonium chloride, tetrabutyl ammonium chloride, tetrahexyl ammonium chloride, tetraoctyl ammonium chloride, benzyltrimethyl ammonium chloride, benzyltriethyl ammonium chloride, phenyltrimethyl ammonium chloride, phenyltriethyl ammonium chloride, cetyl benzyldimethyl ammonium chloride, and hexadecyl trimethyl ammonium chloride. Preferred are alkylamine benzyl quaternary ammonium salts, benzyl triethanolamine quaternary ammonium salts and benzyl dimethylaminoethanolamine quaternary ammonium salts.

In addition, the salt may be a quaternary ammonium or alkyl pyridinium quaternary salt such as those represented by the general formula:

wherein R¹ is an alkyl group, an aryl group or an alkyl group having from 1 to about 18 carbon atoms and B is chloride, bromide or iodide. Among these compounds are alkyl pyridinium salts and alkyl pyridinium benzyl quats. Exemplary compounds include methylpyridinium chloride, ethyl pyridinium chloride; propyl pyridinium chloride, butyl pyridinium chloride, octyl pyridinium chloride, decyl pyridinium chloride, lauryl pyridinium chloride, cetyl pyridinium chloride, benzyl pyridinium and an alkyl benzyl pyridinium chloride, preferably wherein the alkyl is a C₁-C₆ hydrocarbyl group.

The additive may further be an imidazoline derived from a diamine, such as ethylene diamine (EDA), diethylene triamine (DETA), triethylene tetraamine (TETA) etc. and a long chain fatty acid such as tall oil fatty acid (TOFA). Suitable imidazolines include those of formula (IV):

wherein R⁷ and R⁸ are independently a C₁-C₆ alkyl group more preferably hydrido, R⁶ is hydrido and R⁵ a C₁-C₂₀ alkyl, a C₁-C₂₀ alkoxyalkyl group. In a preferred embodiment, R⁶, R⁷ and R⁸ are each hydrido and R⁵ is the alkyl mixture typical in tall oil fatty acid (TOFA).

Suitable mono-, di- and trialkyl as well as alkylaryl phosphate esters and phosphate esters of mono, di, and triethanolamine typically contain between from 1 to about 18 carbon atoms. Preferred mono-, di- and trialkyl phosphate esters and alkylaryl phosphate esters are those prepared by reacting a C₃₋₁₈ aliphatic alcohol with phosphorous pentoxide. The phosphate intermediate interchanges its ester groups with triethyl phosphate with triethylphosphate producing a more broad distribution of alkyl phosphate esters. Alternatively, the phosphate ester may be made by admixing with an alkyl diester, a mixture of low molecular weight alkyl alcohols or diols. The low molecular weight alkyl alcohols or diols preferably include C₆ to C₁₀ alcohols or diols. Further, phosphate esters of polyols and their salts containing one or more 2-hydroxyethyl groups, and hydroxylamine phosphate esters obtained by reacting polyphosphoric acid or phosphorus pentoxide with hydroxylamines such as diethanolamine or triethanolamine are preferred.

The additive may further be a monomeric or oligomeric fatty acid. Preferred are C₁₄-C₂₂ saturated and unsaturated fatty acids as well as dimer, trimer and oligomer products obtained by polymerizing one or more of such fatty acids.

The amount of dithiazine typically introduced into the well is in the range of from about 0.05% to about 5% by volume of the treatment fluid introduced.

Since the dithiazine dramatically reduces corrosion on metal, it may be used in a variety of industrial applications. Since dithiazine has particular applicability in well stimulation processes, such as, acidizing and fracture acidizing, it may be introduced into the well during stimulation. Alternatively, the dithiazine may be introduced prior to or subsequent to, as well as during, a well treatment which produces acid.

Other embodiments within the scope of the claims herein will be apparent to one skilled in the art from consideration of the description set forth herein. It is intended that the specification, together with the examples, be considered exemplary only, with the scope and spirit of the invention being indicated by the claims which follow.

The following examples are illustrative of some of the embodiments of the present invention.

All percentages set forth in the Examples are given in terms of weight units except as may otherwise be indicated.

EXAMPLES

The dithiazine refers to 5-hydroxyethyl-hexahydro-1,3,5-dithiazine of the formula I wherein R is —CH₂CH₂—OH.

Unspent fluid (“UF”) refers to the hexahydro-1,3,5-tri(hydroxyethyl)-s-triazine of the formula II above wherein each R is —CH₂CH₂—OH prior to any spending with hydrogen sulfide.

Whole spent fluid (“WSF”) refers to the homogeneous fluid produced in a hydrogen sulfide scavenger gas scrubbing operation wherein the tower was charged with a triazine[1,3,5-tris(hydroxyethyl)-hexahydro-s-triazine] containing fluid in water and methanol. The fluid contains a high level of the dithiazine, it still being in the WSF.

Isolated dithiazine (“iDTZ”) refers to dithiazine from the WSF that has been separated out of solution in its pure form.

Formulated products were paired using one of the following additives:

-   -   Methyl/Ethylpyridinium benzyl quat (APBQ);     -   Benzyldimethylcocoamine benzyl quat (ABQ);     -   TOFA DETA Imidazoline derivative (“TDID”);     -   Benzyl triethanolaminium quat (BTEAQ); and     -   Benzyl dimethylaminoethanolaminium quat (BDMAEQ).

Formulated WSF refers to the product formed by dissolving the additive in the WSF at a concentration of 12.2 weight percent with methanol at 10 weight percent.

Formulated iDTZ refers to the product prepared by dissolving iDTZ in methanol at a concentration of 9.6 weight percent and then adding to the resultant the additive at a concentration of 19.2 weight percent. This product was then mixed for a brief period while heating to approximately 60° C.

Corrosion rate studies were performed using at ambient temperature a Gamry G Series potentiostat and the conventional Linear Polarization Resistance (LPR) module within the DC105™ corrosion technique software package (Rp/Ec trend). The instantaneous corrosion rate of the three electrode probe system was determined using voltage settings −0.2V to +0.02V versus open-circuit potential, E_(oc). These studies were carried out during an approximately 20-24 hr run time. The treat rates of the corrosion inhibitors were between 50 and 200 ppm. A standard carbon dioxide saturated brine system comprised of 3 weight percent sodium chloride and 0.3 weight percent calcium chloride in 2 liter corrosion cells sparged with carbon dioxide was employed. LPR scans are shown in FIGS. 1-8.

FIG. 1 contrasts the differences at a treatment rate of 500 ppm in corrosion rates between WSF and formulated WSF containing the additive APBQ. As shown, much higher corrosion rates are demonstrated with WSF than formulated WSF.

FIG. 2 contrasts the differences at a treatment rate of 500 ppm in corrosion rates between formulated WSF and UF both containing the additive APBQ. As shown, formulated WSF is a better corrosion inhibitor than UF.

FIG. 3 contrasts the differences at a treatment rate of 430 ppm of WFT and iDTZ. FIG. 3 shows that iDTZ is much more effective than WSF as a corrosion inhibitor.

FIG. 4 contrasts the differences at a treatment rate of 430 ppm of Formulated iDTZ (with the additive APBQ) and iDTZ alone. FIG. 4 shows that Formulated iDTZ is a better corrosion inhibitor than iDTZ alone.

FIG. 5 contrasts the differences at a treatment rate of 430 ppm in corrosion rates between iDTZ alone and Formulated iDTZ (with the additive ABQ), Formulated iDTZ (with the additive TDID) and Formulated iDTZ (with the additive APBQ). FIG. 5 shows the Formulated iDTZ (with APBQ) to be the best corrosion inhibitor. Formulated iDTZ (with TDID) and Formulated iDTZ (with ABQ) demonstrate similar results. All of the formulated iDTZs demonstrated better corrosion inhibition than iDTZ alone.

FIG. 6 contrasts the differences at a treatment rate of 125 ppm in corrosion rates between Formulated iDTZ (with BTEAQ) and Formulated iDTZ (with APBQ). FIG. 6 demonstrates better corrosion results with Formulated iDTZ (with APBQ).

FIG. 7 contrasts the differences at a treatment rate of 125 ppm in corrosion rates between Formulated iDTZ (with APBQ) and Formulated iDTZ (with BDMAEQ). FIG. 7 demonstrates better corrosion results with Formulated iDTZ (with APBQ).

From the foregoing, it will be observed that numerous variations and modifications may be effected without departing from the true spirit and scope of the novel concepts of the invention. 

1. A method of inhibiting corrosion from iron and ferrous base materials during the treatment of a subterranean formation which comprises introducing into a gas or oil well a corrosive inhibiting effective amount of a dithiazine of the formula:

wherein R is selected from the group consisting of a C₁ to C₁₀ saturated or unsaturated hydrocarbyl group or a C₁ to C₁₀ ω-hydroxy saturated or unsaturated hydrocarbyl group for a time sufficient to inhibit corrosion of the iron and ferrous base materials.
 2. The method of claim 1, which further comprises introducing into the well, with the dithiazine of formula (I) at least one component selected from the group consisting of: (a) an alkyl, hydroxyalkyl, alkylaryl or arylamine quaternary salt; (b) a mono or polycyclic aromatic amine salt; (c) an imidazoline derivative; (d) a mono-, di- or trialkyl or alkylaryl phosphate ester; and (e) a monomeric or oligomeric fatty acid.
 3. The method of claim 2, wherein the at least one component is an alkyl, hydroxyalkyl, alkylaryl or arylamine quaternary salt.
 4. The method of claim 3, wherein the quaternary salt of the at least one component is of the formula [N⁺R¹ R²R³R⁴][X⁻] wherein each of R¹, R², R³ and R⁴ contains 1 to 18 carbon atoms and X is Cl, Br or I.
 5. The method of claim 4, wherein at least one of R¹, R², R³ and R⁴ is a C₁-C₆ alkyl group or a hydroxyalkyl group wherein the alkyl group is a C₁-C₆ alkyl or an alkyl aryl.
 6. The method of claim 2, wherein the at least one component is a mono or polycyclic aromatic amine salt with an alkyl or alkylaryl halide.
 7. The method of claim 6, wherein the salt is of the formula [N⁺R¹R²R³R⁴][X] wherein R¹, R², R³ and R⁴ independently contain from 1 to about 18 carbon atoms and X is Cl, Br or I.
 8. The method of claim 7, wherein R¹, R², R³ and R⁴ are independently selected from a C₁-C₆ alkyl group or a C₁-C₆ hydroxyalkyl group or an alkyl aryl group wherein the alkyl group is a C₁-C₆ alkyl.
 9. The method of claim 2, wherein the at least one component is introduced to dithiazine isolated from a spent fluid, the spent fluid having been formed by reaction of hydrogen sulfide and a triazine of the formula:


10. The method of claim 2, wherein the at least one component is introduced to a whole spent fluid containing dithiazine.
 11. The method of claim 2, wherein the at least one component is selected from the group consisting of alkylamine benzyl quaternary ammonium salts, benzyl triethanolamine quaternary ammonium salts and benzyl dimethylaminoethanolamine quaternary ammonium salts.
 12. The method of claim 2, wherein the at least one component is a quaternary ammonium or alkyl pyridinium quaternary salt of the formula:

wherein R¹is an alkyl group or an aryl group having from 1 to about 18 carbon atoms and B is chloride, bromide or iodide.
 13. The method of claim 1, wherein R is —R¹—OH, where R¹ is an alkylene group.
 14. The method of claim 13, wherein R¹ is a C₁-C₆—OH group.
 15. The method of claim 14, wherein R¹ is —CH₂CH₂—OH.
 16. The method of claim 1, wherein the dithiazine is a component of a spent fluid, the spent fluid having been formed by reaction of hydrogen sulfide and a triazine of the formula:


17. The method of claim 16, wherein each R of formula (II) is —CH₂CH₂—OH.
 18. The method of claim 1, wherein the dithiazine is isolated from a spent fluid formed by reaction of hydrogen sulfide and a triazine of the formula:


19. The method of claim 1, wherein the dithiazine is introduced into the well during stimulation.
 20. The method of claim 1, whereby the corrosive effect of an acid solution on metal contacted by an aqueous acid solution is minimized by the addition of the dithiazine to the well. 